Water-soluble disazo dyestuffs



United States Patent O 3,467,645 WATER-SOLUBLE DISAZO DYESTUFFS Heinz Keller, Muttenz, and Hans Grossmann, Oberwil,

Switzerland, assignors to Durand & Huguenin A.G.,

Basel, Switzerland No Drawing. Filed Nov. 6, 1964, Ser. No. 409,589 Claims priority, application Switzerland, Nov. 8, 1963,

13,776/63; Aug. 14, 1964, 10,635/64 Int. Cl. C091) 31/00, 45/24, 39/00 US. Cl. 260--174 1 Claim ABSTRACT OF THE DISCLOSURE Water-soluble metallizable disazo and trisazo dyestuffs corresponding to the general formula Z OZ Y-N=N-RX-RN=NY' I wherein X denotes the direct bond, the radical of a hydrocarbon having 1-7 carbon atoms or a bridge of the formula CO, O, S, SO NH, NHCONH, NHCSNH, NHCO- NHSO N=N-, Y and Y denote the radical of a coupling component comprising the ortho-hydroxycarboxy benzene grouping, which coupling component is selected from the series of the acetoacetamides, S-pyrazolones, benzenes and naphthalenes coupling in ortho-position with respect to a hydroxyl group, Z denotes a hydrogen atom or the group -SO H and R denotes a benzene radical in which the OZ group is in ortho position to the azo group and X is in meta or para position to the azo group and to the group OZ, the dyestuif molecule containing at least 2 groups of the formula SO H.

One representative of dyestuffs of Formula I is produced by tetrazotizing diamines of the general formula ZO oz NHzRXI tNH II wherein R, X and Z have the above said meanings, and allowing them to react with the coupling components comprising the ortho-hydroxy-carboxy benzene grouping, which coupling components are selected from the series of acetoacetamides, 5-pyrazolones as well as benzenes and naphthalenes coupling in ortho position with respect to a hydroxyl group.

The invention relates to new, water-soluble, metallizable disazo and trisazo dyestuffs corresponding to the general formula ZO oz YN=N1'%X t-N=NY I wherein X denotes the direct bond, the radical of a hydrocarbon having 1-7 carbon atoms or a bridge of the formula CO, O, S-, SO NH, NHCONH, -NHCSNH-, NHCO, NHSO N=N, Y and Y denote the radical of a coupling component comprising the orthohydroxycarboxy benzene grouping, which coupling component is selected from the series of the acetoacetamides, S-pyrazolones, benzenes and naphthalenes coupling in ortho-position with respect to a hydroxyl group, Z denotes a hydrogen atom or the group -SO H and R denotes a benzene radical in which the OZ group is in ortho position to the azo group and X is in meta or para position to the azo group and to the group OZ, the dyestuif molecule containing at least 2 groups of the formula SO H.

One representative of dyestuffs of Formula I is the dyestuff of the formula HOgSO 3,467,645 Patented Sept. 16, 1969 It is already known to produce metallizable disazo and trisazo dyestuffs by tetrazotizing aromatic diamines containing a hydroxyl group or sulfuric acid semi-esters thereof in ortho position to the amino groups and joining them with S-pyrazolones, preferably with naphthols, which couple in ortho position to a hydroxyl group. A further known method consists in allowing agents, which are capable of withdrawing heavy metals from heavy metalscontaining compounds, to react with disazo or trisazo dyestuffs which contain such heavy metals, in particular copper in complex form, and which were obtained by using tetrazotized diamines as starting products.

It has now been found that new and particularly valuable water-soluble, metallizable disazo and trisazo dyestuffs of Formula I are obtained by tetrazotizing diamines of the general formula Z O 0 Z wherein R, X and Z have the above said meanings, and allowing them to react with the coupling components comprising the ortho-hydroxy-carboxy benzene grouping, which coupling components are selected from the series of acetoacetamides, S-pyrazolones as well as benzenes and naphthalenes coupling in ortho position with respect to a hydroxyl group.

Dyeings can be produced with the dyestuffs obtainable according to the invention which, compared to dyeings produced with comparable known dyestuffs, are superior primarily with regard to fastness to wetting.

The following compounds are examples of suitable diamines for this process: 3,3'-dihydroxy-4, 4'-diaminodiphenyl, 4,4'-dihydroxy-3,3-diamino-diphenyl, 4,4'-dihydroxy 3,3 diamino diphenylmethane, 4,4 dihydroxy -3,3 diamino diphenyl 1,1 cyclohexane, 4,4- dihydroxy 3,3 diamino diphenyl 1,1 ethane, 4,4- dihydroxy 3,3 diamino diphenyl 2,2 propane, 4,4-

'dihydroxy-3,3'-diaminodiphenylsulfone and disulfuric acid semi-esters thereof. The tetrazotization of the diamines of Formula II can be effected according to known methods.

Suitable coupling components according to the definition given are those whose ortho-hydroxycarboxy benzene grouping, which may be further substituted if desired, is itself capable of coupling, such as 2,4- and 2,5-dihydroxy benzoic acid, or is bonded across a bridge to a coupling component conventional in azo chemistry. Numerous compounds of this kind are already known or can be produced by methods known per se. The following typical examples may be mentioned: 5-acetoacetylamino-2-hydroxy-benzoic acid, 'I-(4'-hydroxy-3-carboxyphenyl)3- methyl 5 pyrazolone, 1-(4'-hydroxy-3-carboxybenzene sulfonylamino) 8 naphthol 3,6 disulfuric acid, 2-(4'- hydroxy 3' carboxy phenylamino) 5 naphthol 7- sulfonic acid, 2-naphthol-6-sulfonic acid-(3-hydroxy-4- carboxyphenyl) ester, 2 (4 hydroxy 3 carboxyphenyl) 5' hydroxy (naphthol 1,2':4,5-triaz0l) 7'- sulfonic acid.

The coupling of the tetrazo compounds with the coupling components as defined is effected according to methods known per se. In order to obtain better coupling and/or better water-solubility of the coupling products it is often advisable to use the disulfuric acid semi-esters of the o,o-dihydroxydiamines.

A further process for preparing dyestuffs of Formula I consists in treating by conventional methods disazo 0r trisazo dyestuffs containing heavy metals, which comprise COOH complex-bound copper preferably on the azo bridge and, when unmetallized, correspond to Formula I (Z=H) with agents capable of withdrawing heavy metals, for example with the aid of sulfide ions or concentrated mineral acids. The heavy metal complexes used as starting substances in this process are obtained, for example, by the dealkylating or dehalogenating action of agents capable of withdrawing heavy metals, in particular copper yielding agents, on coupling products resulting from tetrazotized o,o-dialkoxyor o,o'-dihalodiamines and coupling components according to the definition given. Suitable diamines of this type are, for example, 1,1-(3,3'-dimethoxy-4,4'-diaminodiphenyl)-cyclohexane, 3,3-dichloro-, 3,3'-diethoxy-, and preferably 3,3'-dimethoxy-4,4'-diaminodiphenyl. A particularly advantageous process for preparing the copper complexes used as starting substance consists in many cases in allowing an oxidizing agent and a copper-yielding compound to act simultaneously in known manner on disazo dyestuffs obtained from tetrazotized diamines being free in ortho position of complex-forming groups and from the defined coupling components, thus introducing a second hydroxyl group in ortho position to each azo bridge. This process is employed especially when the corresponding diamines containing in ortho position, a hydroxyl group or a substituent convertible into a hydroxyl group are not available or only difficultly available or when the coupling does not take place in the desired manner.

The following compounds are, for example, suitable diamines for the latter said process: 4,4'-diamino-diphenyl-oxide, 4,4-diamino-diphenyl-sulfide, 4,4-diaminodiphenyl urea, 4,4-diamino-diphenyl-thiourea, 4,4 diamino diphenyl methane, 4,4 diamino diphenyl- 1,1 cyclohexane, 4,4 diamino diphenyl 2,2 propane, 4,4-diaminotriphenylmethane, 4,4-diaminobenzophenone, 3,3'-, 4,4'-, or 3,4-diaminobenzanilide, 3,3'-, or 3,4-diaminobeuzenesulfanilide, 4,4-diaminodiphenyldisulfonic acid, 4,4'-diaminodibenzyl-disulfonic acid, 4,4- diaminostilbene-IZ,2'-disulfonic acid, 4,4-diaminoazobenzene.

In the disazo and trisazo dyestuffs of Formula I, Y and Y may be the same or different according to whether 1 mole of a tetrazotized diamine is combined with 2 moles of the same coupling component or stepwise with 1 mole each of two different coupling components.

The starting substances are selected according to the invention such that the resulting disazo dyestuffs contain at least two groups of the formula SO H present as sulfonic acids and/or as sulfuric acid semi-esters. The dyestuffs of Formula I are further obtained also by allowing sulfonating or sulfatizing agents to react with dyestuffs of Formula I which, if desired, may be free of SO3H groups.

The metallizable disazo and trisazo dyestuffs of Formula I which are obtainable according to the invention are generally readily water-soluble. They are suitable for dyeing and printing the most varied materials, such as leather, anodically produced oxide layers on aluminum, animal, vegetable and synthetic textile fibers, particularly cellulosic fibers such as cotton, linen, rayon or staple fibre from regenerated cellulose. The dyeings are considerably improved with regard to their general fastness properties by the action of agents yielding heavy metals, preferably yielding chromium or copper. An advantageous application process consists in allowing chromiumand copper-yielding agents to act simultaneously or subsequently on the dyeing. For example, a material pretreated with chromium-yielding compounds can be dyed and thereafter cuprated or a direct dyeing can be subsequently treated in an aqueous bath containing a mixture of chromiumand copper-yielding agents. A particularly suitable process for the application of the inventive dyestuffs consists in applying a printing paste prepared in conventional manner containing inter alia a dyestuff of Formula I and a chromium-yielding compound to a fabric and treating this latter after drying and steaming in a bath containing a copper-yielding compound. When using special copper-yielding compounds, for example copper rhodanide, the copper-yielding compound can also be added to the printing paste in chrome printing, a post-treatment thereby becoming superfluous. The chromium preferably enters in the ortho-hydroxycar boxyl and the copper preferably in the o,o'-dihydroxy azo group, any sulfuric acid semi-esters present being simultaneously split. The dyeings obtained in this manner are characterized generally by good light fastness, particularly however by very good fastness to wetting.

Heavy metal complexe of dyestuffs of Formula I can further also be prepared in substance according to generally known methods. By heavy metals such metals are to be understood which are capable of forming stable metal chelates with the dyestuffs of Formula I, for example manganese, iron, nickel, and particularly chromium, cobalt and copper.

A particularly suitable process consists in treating dyestuffs of Formula I in substance with heavy metal yielding agents. Heavy-metal-yielding compounds are, for example, the hydroxides, oxides, halides, sulfates, nitrates and acetates of the said heavy metals. However, compounds can also be used which contain the metals in complex form, for example oxalates, tartrates, salicylates and amino complexes. The treatment of the dyestuffs with heavy metal-yielding agents can be effected both in aqueous medium at various pH-values and in an organic solvent such as formamide, dimethylformamide, ethylene glycol and ethers thereof. The metallization is advantageously effected in the heat, open or under pressure, for example at boiling temperature of the reaction mixture, with or without the addition of agents affecting the complex formation, for example alcohols, pyridines, alkanolamines. In the event that the metal present in the heavy metal-yielding agent has a different valence the reaction can be performed in the presence of a reducing agent or oxidizing agent, respectively, such, for example, as is the case, when chromating with chromates in the presence of glucose. The reaction mixture can be present in the form of a solution, suspension or paste. The conversion into the metal complex compound can also take place with a dyestuff such as is present in the coupling mixture. If desired, mixtures of various dyestuffs can be treated with heavy metal-yielding agents or one dyestutf can be treated with a mixture of heavy metal-yielding agents.

The dyestuffs of Formula I are characterized inter alia by comprising two different types of chelate-forming groups. According to the type of dyestuff, of the heavy metal-yielding agent and the reaction conditions, such as e.g. pH-value of the reaction mixture or ratio of compounds employed, the heavy metal is complex-bonded to both o,o'dihydroxyazo and/or to both o-hydroxycarboxy groups. The ratio of metal to chelate-forming group in the metal complex can be 1:1 or 1:2.

The conditions are advantageously selected such that water-soluble dyestuffs are formed which contain the heavy metal in complex form with the o,o-dihydroxyazo groups and whose o-hydroxycarboxy groups are exempt of heavy metal. Such dyestuffs are further obtained by treating dyestuffs containing complex-bonded heavy metal on both chelate-forming groups with compounds which withdraw complex-bonded metal only from the o-hydroxycarboxy groups but not from the o,o-dihydroxyazo groups. Such compounds are e.g. sarcosine, ethylene diamine tetraacetic acid and nitrilotriacetic acid.

The heavy metal complex dyestuffs of the invention are also obtained according to the methods cited hereinbefore, such as e.g. action of heavy metal-yielding agents on o-alkoxy or o-halo-o'-hydroxyazo dyestuffs or by the action of copper-yielding agents on o-hydroxyazo dyestuffs in the presence of an oxidation agent.

Particularly valuable dyestuffs are obtained by allowing agents yielding a coordinative hexavalent metal, particularly cobalt or chromium, to react in such manner with dyestuffs of Formula I that one atom of metal complex-binds two o,o'-dihydroxyazo groups.

The heavy metal complexes of Formula I obtainable according to the invention are suitable for dyeing the most varied materials, such as anodically produced oxide layers on aluminum, leather, animal, vegetable and synthetic textile fibers, especially cellulosic fibers such as cotton, linen, rayon and staple fiber. Insofar as the metal complex compounds also comprise free chelate-forming groups, the dyeings thereof can be improved by an aftertreatment on the fiber with heavy metal-yielding agents. In particular, the dyestuffs of Formula I which contain complex-bonded metal only on the o,o-dihydroxyazo group are suitable for the so-called chrome printing. Dyeings are obtained which are primarily characterized by excellent fastness to light, water and washing.

The invention will be described by reference to the following examples, but is not intended to be restricted thereto. In the examples, all parts are parts by weight and the temperature is given in degrees centigrade.

Example 1 37.6 parts of disulfuric acid semi-ester of 3,3'-dihydroxy-4,4'-diaminodiphenyl are neutralized in 350 parts of water, diluted with 13.8 parts of sodium nitrite and flowed into a mixture of 200 parts of sodium chloride, 400 parts of finely ground ice and 58 parts of hydrochloric acid (33%). The suspension is stirred at 5 until the tetrazotization is terminated and an ice cold solution of 51.9 parts of 1-(4-hydroxy-3'-carboxybenzene sulfonylamino)-8-naphthol-3,6-disulfonic acid and 54 parts of sodium hydroxide solution (31%) in 300 parts of water is then added. After 30 minutes a mixture of 37.5 parts of 2 (4 hydroxy 3' carboxyphenylamino) 5- naphthol-7-sulfonic acid, 27 parts of sodium hydroxide solution (31%) and 150 parts of water is added. One first stirs while cooling, then at room temperature, until the coupling is terminated, heats to 60 and separates off the disazo dyestufi by the addition of sodium chloride. The dyestuif is obtained pure by dissolving and precipitating from aqueous alcohol and water.

In the form of the free acid it corresponds to the formula HOaSO HO SOaH HOgSO t a S- HOaS- and dissolves in water to give a bluish violet colour, in concentrated sulfuric acid to give a greenish blue colour and in diluted sodium hydroxide solution to give a reddish violet colour.

2 parts of this dyestulf and 10 parts of urea are dissolved warm in 32 parts of water and stirred into 50 parts of a tragacanth thickener (5%). After cooling, 6 parts of an aqueous chromium acetate solution containing 6% chromium are added and the paste is printed on a cotton fabric. After drying, steaming for 8 minutes and rinsing, the fabric is after-treated for one minute at 80 in a bath containing 0.5% of crystallized copper sulfate and 0.3% of acetic acid, and finally treated in the conventional way. A navy blue dyeing is obtained which is characterized by excellent fastness to light and very good fastness to washing.

Substantially the same dyeing is obtained if the corresponding sulfuric acid ester-free dyestuff is employed.

Example 2 A mixture of parts of 2(4-hydroxy-3'-carboxyphenylamino)-5-naphthol-7-sulfonic acid, parts of sodium hydroxide solution (31%), 50 parts of a-picoline, 10 parts of the sodium salt of naphthalene-Z-sulfonic acid and 300 parts of water is introduced at 0 into a tetrazo suspension produced according to Example 1 from 37.6 parts of disulfuric acid semi'ester of 3,3'-dihydroxy-4,4'- diaminodiphenyl. One first stirs while cooling, then at room temperature, until the coupling is terminated. The dyestuff is separated off by the addition of sodium chloride, filtered and purified by dissolving and precipitating from aqueous alcohol.

The resulting dyestuff corresponds in the form of the free acid to the formula OSOsH 80% acetic acid, a navy blue dyeing having excellent fastness properties to light and washing is obtained.

Example 3 37.6 parts of the disulfuric acid semi-ester of 4,4- dihydroxy-3,3-diamino-diphenyl are tetrazotized in analogous manner to Example 1. A mixture of 36 parts of 2,4- dihydroxy benzoic acid, 40 parts of sodium carbonate, 30 parts of sodium bicarbonate and 200 parts of water is added at -5 to the tetrazo suspension, After termination of the coupling the precipitated dyestutf is filtered.

The resulting dyestuif corresponds in the form of the free acid to the formula OSOaH (RH and dissolves in water to give a brownish red colour, in concentrated sulfuric acid to give a dark reddish brown COOH 7 8 colour. The dyestuff yields in chrome printing on staple of 2-(4-hydroxy-3'-carboxy-benzene-sulfonylamino) 8 fibre after-coppered according to Example 1, a brownnaphthol-6-sulfonic acid, 55 parts of sodium hydroxide ish violet dyeing having very good fastness properties. solution (31%) and 200 parts of water. After termina- A dyestuff having similar properties is obtained if 2,5- tion of the coupling the dyestuff is separated off by the dihydroxy benzoic acid is used instead of 2,4-dihydroxy addition of hydrochloric acid and converted into the benzoic acid. sodium salt. The resulting dyestult corresponds in the form The disulfuric acid semi-ester of 4,4-dihydroxy-3,3- of the free acid to the formula (IJII (|)H OH OH IIOO( J sour soz notsdooii diaminodiphenyl used in this example is prepared as foland yields in chrome printing on cotton a reddish violet lows: 27.6 parts of 3,3-dinitro-4,4-dihydroxydiphenyl dyeing having very good fastness to washing, when after- (prepared by nitrating 4,4-dihydroxy-diphenyl) are introcoppered. I duced into a mixture of 280 parts of chlorosulfonic acid The diamine used in obtained by nitrating and reducand 1400 parts of ot-picoline, heated for 4 hours at 80 ing 4,4-dihydroxy-diphenylsulfone. and thereupon flowed within one hour at boiling tempera- Example 6 ture into a mixture of 400 parts of pulverized iron, 400 A. mixture of 1L7 parts of the disazo dyesmfi from Parts of a h 30 Parts of hydrochlorlc acld (33% tetrazotized 3,3-dimethoxy-4,4'-diamondiphenyl and 2' The reduction mixture is then rendered alkaline to phenol- (N 4' hydmxy 3I CarbOXy benZene sulfonyl N methyl Phthalethe by sprmkhng Sodlum carbonhte and filtered amino)-8-naphthol-6-sulfonic acid, 300 parts of water, 4.4 boiling hot. The disulfuric acid semiester is separated off parts f diethanolamine, 8 parts of glycerine 16 parts of y the addition of 100 Parts of Sodium chloride to the ammonia (22%) and 5 parts of crystallized copper sulfate filtrate, filtered and dried. is refluxed for 50 hours. The o-hydroxycarboxy copper Example 4 compound which first forms is thereby converted into the o,o-dihydroxyazo copper compound, with the splitting off of the dimethoxy group. The resulting copper compound is filtered and 500 parts of Water are diluted with a sodium 41.8 parts of the disulfuric acid semi-ester of 2,2-(4, 4dihydroxy-3,3-diaminodiphenyl)-propane are tetrazotizg? i g h g z g gf Sulfide solution at until dissolved sulfide ions are t 0 Into a thhtthre of Pdrtb O y roxy' detectable. After filtering the copper sulfide, the metal-free carboxy-p y -PY 80 Parts f dyestuff is precipitated by the addition of sodium chloride, um carbonate and 600 parts of water. After termination dissolved and precipitated from water and dried.

t "5 0f the eeuphhg the flyestuft l5 Separated Otf by the addl u The resulting dyestuff corresponds in the form of the tion of sodium chloride and filtered. free acid to the formula OH OH OH 011 C (7113 l l l CH3 i OOH iio-som x=xh-sm-O-no llOOJ -SO3H 1 0 s The resulting dyestufi eoffespehds in the form Of the and dissolves in water, when concentrated, to give a greenfrce acid to the formula ish blue colour, and when diluted to give a reddish blue H0350 OSOslI (HI l on /C=CN=NC N=1 t \@/C t t N=C C=N 11000 I CH3 CH3 t oooir CH3 CH and dissolve in Water to g Y Orange c010th colour, Whereas on dissolving the dyestuft' in concentrated and in concentrated sulfuric acid to giv a r d C sulfuric acid it yields a greenish blue colour and in diluted The dyestutf yields on cotton an orange dyeing hav ng sodium hydroxide solution a violet colour. The dyestuff excellent fasteness to washing in chrome printing, when yields in chrome printing on rayon a marine blue characafter-coppered. A golden yellow dyeing is obtained on terized by excellent fastness to light and very good fastness anodieally oxidized aluminium after sealing with nickel to washing when after-coppered in the way disclosed in acetate. the above Example 1.

Dyestuffs havlhg almost t e Pf p are h- Substantially the same dyestutl is obtained by heating ef e y ez h f t e acid seml-estel 0f in hydrochloric acid solution the disazo dyestuif obtained 4 Y Y' -d1aII11h0-d1PhehY1)ethane S from tetrazotized disulfuric acid semi-ester of 3,3'-dihyhexane droxy-4,4-diaminodiphenyl and from the coupling com- The disulfuric acid semi-ester used in this example is obtained in an analogous process to that described in Example 3 starting from 2,2-(3,3-dinitro-4,4"-dihyponent used in this example, the sulfuric acid ester groups being split hydrolytically.

droxydiphenyl)-propane by sulfating and reducing or by Example 7 the action of chlorosulfonic acid in chloroform on 2,2-(4', 127.4 parts of the disazo dyestuff from tetrazotized 4-dihydroxy-3',3"-diaminodiphenyl)-propane. 4,4'-diaminodiphenyl-2,2'-disulfonic acid and 4-hydroxy- Example 5 3' carboxy 2 (3 methyl 5" oxo pyrazolin 1"- 13 3 parts f sodium nitrite dissolved in 50 parts f yl)-diphenylsulfone-4-sulfonic acid are dissolved neutral water are ll to d i at 10 i a mixture f 2 in 1500 parts of water. After the addition of 50 parts of parts of 4,4'-dihydroxy-3,3-diaminodiphenylsulfone, 50 crystallized pp Sulfate, 25 Parts of hydrogen Peroxide parts of hydrochloric acid (33%) and parts of water. in 500 Parts Of Water are allowed to p in at The After 30 minutes the tetrazo compound is filtered and inprecipitated copper compound is denietallized with sodium troduced at room temperature into a mixture of 87.8 parts sulfide as described in Example 6.

The resulting dyestuff corresponds in the form of th free acid to the formula and yields, in chrome printing on cotton and when aftercoppered, a brownish orange having good fastness properties to light and washing. The dyestuff dyes prechromated wool and silk, after-coppered, in brownish yellow shades.

If equivalent amounts of the disazo dyestuff from tetrazotized 4,4'-diaminostilbene-2,2'-disulfonic acid and 2-(4' hydroxy 3 carboxybenzene sulfonylamino) 8 naphthol-6-sulfonic acid are used in this example, a dyestuff is obtained which yields, in chrome printing on cotton and when after-coppered, a violet dyeing. Dyestuffs having similar properties are obtained if the 4,4'-diaminostilbene- 2,2-disulfonic acid is replaced by 4,4'-diaminodibenzyl- 2,2-disulfonic acid or by 1,1-(4,4'-diaminodiphenyl) cyclohexane.

Example 8 65 parts of chlorosulfonic acid are allowed to drop into 600 parts of pyridine at 2030 while cooling. Thereafter 95.6 parts of the disazo dyestuff from tetrazotized 3,3- dihydroxy 4,4 diaminodiphenyl and 2 (4 hydroxy- 3' carboxy benzene sulfonylamino) 7 naphthol are introduced during one hour. One heats for 6 hours at 65, pours the esterification mixture into soda solution (10%) and distills off the pyridine under vacuum. The precipitated dyestuif is filtered and dissolved and precipitated from water.

The resulting dyestulf corresponds in the form of the free acid probably to the formula I COOH and dissolves in water to give a violet colour and in concentrated sulfuric acid to give a greenish blue colour.

A cotton fabric is impregnated with a mixture of 2 parts of this dyestuif, 10 parts of urea, 0.5 part of sodium chloride, 10 parts of a tragacanth thickener (6% 4 parts of an aqueous chromium acetate solution containing 6% of chromium, and 80 parts of water. After drying, steaming for 8 minutes and rinsing, the fabric is after-coppercd according to Example 1. A reddish blue dyeing having very gOOd fastness to washing is obtained.

Further metallizable disazo dyestuffs obtained according to the processes described in the preceding examples are listed in the following table. In the column. Shade, the shade of the dyeing produced according to Example 1 on cotton is given.

TABLE Example Y and T Z X Shade 9 Y and Yz2A-dihyroxybenz0ic acid Greyish violet,

Y and Y:fi-acetoacetylamino-2-hydroxybenzoic acid. S0311 Brown, Y and Y:4Jaydroxy-W-carboxy-Z-(3"-methyl-5"-oxopyrazolm-l -yl)-d1phenylsulione- SOQH Reddish violet.

sulfonic aci Y and Y:1-(4-hydroxy-3-carboxybenzenesullonylamino) -8-naphth0l-3,6-diSuli0nic acid- S0311 Blue. Y and Y:2-(4-hydroxy-3-carb0xybenzenesulfonylamino)-5-naphthol-7-sulfonic acid"..- 8031']: Vi l t, 14. Y and Yz2-(4-hydroxy-3-carboxybenzenesulfonylamino)-8-naphthol 4,(i-disulfonic acid SO3H Blue. Y and Y:1-(4-l1ydr0Xy'3-carboxybenzenesulfonylamino) 8-naphth0l-4-suli0nic acid S0 11 Turquoise bl 16 Y and Y:2-(N-4-hydroxy-3-carboxybenzenesulfonyl-N-methylamino) -8-naphth0l-6- S0311 Reddish blue.

sulfonic acid. 17 Y and Y:3-(8-hydr0xynaphthyl-1amin0)-propi0nic acid-(4-hyd.roxy-3"-carboxyphenyl- S0 11 Bluish green,

amide)-3,6-disulfonic acid. 18 Y and Y:2-(4-hydroxy-3-ca.rboxybenzenesulionylacetylannno)-5-naphthol-7-sulf0n1c SOQH Reddish blue.

acid. 10 Y and Y:N-4-hydroxy-3-carboxyphenyl-N-fi-hydroxynaphthyl-(2)-urea-7-sulionic acid SOgI-I Do. 20 Y and Y:5-(2-naphthol-6-sulionylamino)-2-hydr0xybenzoic acid SOQH Violet. 21 Y and Y:4-(2-naphthol-fi-sulionyloxy)-2-hyd1'cxybenzoic acid SOKH Do. 2 Y2As in Example 12, Y:5-(1-naphthol-4-sulfonylamino)-2-hydr0xybenz0ic ac1d SO H Blue, 23 YzAs in Example 14, Y:as in Example 21 SO31): Do. 24 YzAs in Example 12, Y:1-(4hydroxy-3-carboxyphenyl)-5-pyrazolone-3-carb0xylic acid. SOQH Reddish blue. 25 Y:As in Example 12, Yzas in Example 9. 0 H Bluish green. 26 Y and Y:1-(N-4-hydroxy-3-carboxybenzenesulionyl-N'ethylamino)-8-naphthol-3,G- H Blue.

disulfonic acid. 27 Y:5-acetoacetylamino-2-hydroxybenzoic acid-3-sulfonic acid, YrAs in Example 13 H Violet. 28 Y and Y:l-(3-nitro-2-mcthyl-4-hydroxy-5-carboxybenzene-sultonylamino)-5-naphthol- II Blue.

7-su1i0nic acid. 29 Yz2-(N -4-hydroxy-3-carboxybenzenesulfonyl-N-B-hydroxy-(l-suli0napl1thyl-2amino)- H D ethane-Lsulfonic acid, YzAs in Example 20. 30 Y and Y:2-(4-hydroxy-3-carboxyphenyl)-5-hy 1roxy-(naphto-12:4,5-tnazol)-7-sulfon1c H Navy blue.

acid.

Example Y and Y Z X shade 31 Y and YtAs in Example 13 II O Violet. Y and Y:fi acetoacetylamino-Z-hydroxybenzoic acid-3-sulfonic acid H -CO Brown.

Y and YzAs in Example 16 H SO Violet.

Y and YzAs in Example 13.- H C6l'f10 Do. Y and YzAs in Example 13.. II -CH(CaII) Do. 36 Y and YzAs in Example 11 H -CH2' Yellowish. 37 Y and Y:1-(4'41ydr0xy-3-carboxybenzenesulfouylacetylamino)-8-naplithol-3,G-tlisul- H -HNCSNH Violet.

tonic acid.

Z O 0 Z l l xr- :\v; :\ww.

38 Y and Y:2-(4-l1ydroxy-3-carboxybenzenesulfonylamino)-8-naphth0l-6-sullonic acid 11 Bordeaux. 39...- Y and YzAs in Example H Reddish Brown. 40.... Y and Y:1-(2hydroxy-3-carboxyphenyl)-3-1netliyl-5-pyrazolone-5-sulfonic acid H SOz- Brownish yellow. 41 Y and Y:(1-(5-cliloro4-hydroxy-3-carboxybenzenesulfonylamino)8-naphthol-3,6-disul- H -SOg-- Violet.

ionic aci 42 Y and Y:As in Example H -NHCONlI- Brownisli yellow. 43 Y and Y:1-(4-liydroxy-3-carboxyplienyl)-3-methyl-5-pyrazol0ne II -NI-ICO- Brownisli orange. 44.. Y and Y:As in Example 12 S0311 CsI'Ii0 Violet.

Y and Yz4-aeetoacetylamin S0313]: -C(CH3)- Golden yellow. Y and YzAs in Example 9. S0311 CHCH Rcddish brown.

Y and Y:As in Example 1 S03H -C(CH3)z- Violet.

O a S0311 DO. Y and YzAs in Example 9 H -C(CH;): Reddish brown. 50 Y and Y :As in Example 11 S0211 C(CH Orange. 51 Y and YzAs in Example S0311 CH2 BIOWIilSll yellow.

Example 52 44 parts of 3:3 diamino-4:4-dihydroxy-diphenylsulfone-5:5-disulfonic acid are diazotized indirectly in known manner and combined at 0 with a solution of 80 parts of 2 (4'-hydroxy-3'-carboxyphenylamino)-5-naphthol-7-sulfonic acid, 67 parts of sodium hydroxide solution (30%) and parts of sodium carbonate in 400 parts of water. After termination of the coupling the resulting disazo dyestutf is separated off by the addition of sodium chloride, filtered and dried.

The resulting dyestuif dissolves in water to give a reddish violet colour and in concentrated sulfuric acid to give a bluish violet colour. The dyestufi? yields in chrome printing on staple fiber a navy blue dyeing having very good fastness properties.

The diazo components used in this example are obtained by sulfonating 4:4-dihydroxydiphenylsulfone with concentrated sulfuric acid, nitrating with mixed acid and reducing according to the Bchamp method.

If the coupling component is replaced in this example by equivalent amounts of 2:4-dihydroxy benzoic acid a brownish red dyeing is obtained, and, if 1-(4'-hydroxy-3- carboxyphenyl)-3-methyl-5-pyraz0lone is used, an orange 4 dyeing having similar fastness properties is obtained.

Example 53 121.3 parts of the dyestufiE according to Example 52 (molecular weight 1213) are dissolved in 2500 parts of water at 80 and diluted with 40 parts of cryst. copper dissolves in water to give a violet colour, in concentrated sulfuric acid to give a red colour, and yields in chrome printing on cotton, silk and wool a violet dyeing having excellent fastness to light and Washing.

If equivalent amounts of nickel acetate are used in this example instead of the copper acetate, a dyestuff is obtained which has similar dyeing properties.

Example 54 121.3 parts of the dyestuff according to Example 52 (molecular weight 1213) are dissolved at 130 in 1500 parts of formamide. 25 parts of a chromium acetate containing 24.1% of chromium are thereafter added and the solution is stirred for 5 hours at 130. After diluting with 500 parts of water, the dyestuff is precipitated by the addition of sodium chloride, filtered at 20 and dried.

The resulting dyestuff, which contains 1 atom of complex-bonded chromium on two azo groups, dissolves in water to give a blue colour, in concentrated sulfuric acid to give a bluish red colour and yields in chrome printing on cotton a bluish grey dyeing having excellent fastness to washing. Similar shades are obtained in chrome printing on a polyamide fabric.

Example 55 121.3 parts of the dyestulf according to Example 52 (molecular weight 1213) are dissolved at 70 in 2000 parts of water. A solution of 26 parts of cryst. cobalt acetate (molecular weight 249) in 1000 parts of water is allowed to drop in within 90 minutes and the solution is stirred for minutes at The dyestuff is separated off by the addition of 800 parts of potassium chloride, filtered at 20 and dried.

The resulting dyestufI dissolves in water to give a violet-toned grey colour, in concentrated sulfuric acid to give a bluish red colour and yield in chrome printing on cotton a reddish grey dyeing which is characterized by 13 14 very good fastness to light and excellent fastness to fonylamino) 8 naphthol 3,6 disulfonic acid. 14.4 washing. parts of this disazo dyestufi (molecular weight 1436 Example 56 moles) and 10 parts of sodium acetate are dissolved in 400 parts of water. An aqueous solution of chromium acetate containing 0.52 part of chromium is thereafter allowed to drip in and the mixture is refluxed for 10 hours. The dyestufi is separated otf by the addition of potassium chloride, filtered and dried.

The resulting dyestuff dissolves in water to give a blue 10 colour, in concentrated sulfuric acid to give a bluish green colour and yields in chrome printing on cotton a slightly greyish blue dyeing having very good fastness properties.

The same dyestufi is obtained according to the process described in Example 6, if the symmetrical disazo dyestuff obtained from tetrazotized 3,3-dimethoxy-4,4'- diamino-diphenyl and from the coupling component used 12.7 parts of the trisazo dyestuff from tetrazotized 4,4- diaminoazo benzene and 1-(4-hydroxy-3-carboxyben- 5 zene sulfonylamino) 8 naphthol-3,6-disulfonic acid (molecular weight 1272) are dissolved at 50 in 1000 parts of water. After adding 5.5 parts of cryst. copper sulfate and 10 parts of cryst. sodium acetate, 2.7 parts of hydrogen peroxide (100%) dissolved in 150 parts of water are allowed to drip in at 50 during 2 hours. By the addition of 200 parts of potassium chloride, the resulting complex copper compound is separated 01f, filtered and dried.

The resulting dyestutf which presumably corresponds in the form of the free acid to the formula H033 SOsH HOaS- S dissolves in water to give a bluish 0010111, in sulfuric acid in the above gxample, is coppered, while demethylating,

to give a bluish grey colour and yields in chrome printing h decoppered d h t d,

0H Cotton 21 fast y bllle- If the chromium acetate is replaced in this example by The Same dyestuff 1S q p y g y 4 parts of crystallized copper acetate (molecular weight Stuff from 1 mole of dlazotlled 5-nltl'o-2-amllloanlsol 199.7), a dyestutf is obtained which yields fast blue dyeand 1 mole Of the coupling component IlSBd in this ings in chrome printing on cotton,

example with the aid of glucose and coppering the resulting trisazo dyestuif according to Example 6, thus Example 59 demethylating the dyestulf. 7.7 parts of the dyestuif of the formula Example 57 3F 3 1 3 1 0 11.7 parts of the disazo dyestuff from 1 mole of OH tetrazotized 3,3'-dimethoxy-4,4'-diaminodiphenyl and 2 moles of 1-(2'-methyl 4' hydroxy-S-carboXy-benzene sulfonylamino)-5-naphthol-7-sulfonic acid, 25 parts of HO N N SO N N OH ammonia (22%), 7 parts of cryst. copper sulfate and 4 H000 00011 200 parts of water are refluxed for 40 hours. The resulting copper complex compound is separated 01f by the (molecular weight 770) and 10.9 parts of the dyestuff addition of sodium chloride, filtered and 150 parts of of the formula S0 11 S0311 OH 0H OH HO 5 HO- OH I H000 N C-N COOH I /CN=N SO2- N=NO\ e fi= HOaS CH3 CH3 SOaH water in the presence of 2.5 parts of nitrlotriacetic acid (molecular weight 1090) are dissolved in 300 parts of heated to 80 for 30 minutes. The dyestuif is recovered water. After adding an aqueous solution of chromium as usual. acetate containing 1.04 parts of chromium, one refluxes The resulting dyestulf which in the form of the free to boiling point until the chromation is terminated. The acid presumably has the formula (|)-Cu0 0 Cu0 l T HOOCII sou-1 HOaS- COOH HO-O-SOQNH NHSOa-OOH l (7H3 CH3 yield a light-fast blue when y irectly on cotton. dyestulf is separated 01f by the addition of sodium chlo- The fastness to washing of the dyeing is substantially ride, filt r d and dried.

improved by an after-treatment at 80 for 30 minutes in The rasulting dyesmif dissolves in Water to give a a bath contammg 4% of chromlum acetate and 4% of brownish red colour, in concentrated sulfuric acid to formlc give a yellow colour and yields in chrome printing on Example 58 The disazo dyesmfi is prepared Similarly to Example cotton a brownish red dyeing having excellent fastness 2 by tetrazotizing 1 mole of the disulfuric acid semi-ester Propertles to hght and Washmg' of 3,3 dihydroxy-4,4 diaminodiphenyl and coupling Further heavy metal Complex 310 dyestuffs Obtained with 2 moles of 1-(4'-hydroxy-3'-carboxy-benzene-sulaccording to the processes described in the preceding examples are listed in the following table. In the column Metal, the metal linked in a complex form with the 0,o'-dihydr0xyazo groups is given and in the column 56.

Shade, the shade obtained in chrome printing on cot- What we claim is: ton, is shown. 5

Coupling component (2 moles) Example Tetrazo component (1 mole) Obtained by the action of copper-yielding agents in the presence of an oxidation agent analogous to Example Metal Shade 6O 3:3"diamino4Adihydroxy-diphcnyl-sulfone-5:5- 1-(2-hydroxy3-carboxyplienyl)-3methyl-5-pyrazo1onc Cu Yellow.

disulionic acid. 5-sulionic acid.

d .do. Do. do... Orange. hy Brown. 1-(4-hydroxy-3-carboxybci Reddisli violet.

naphthol-3:6-disulionic acid.

d Greyish violet.

Reddish grey. Reddish violet. Bordeaux.

Do. Brownish. -hydroxybenzoic acid-5sulfonic Brownish yellow.

72 Disuliuric acid semi-ester oi 3:3-dihydroxy-4:4- 2-(4-hydroxy-3-carboxybenzene-sull'onylamino)-8- Cu Navy blue.

diaminodiphcnyl. naphthol-G-suli'onic acid.

73 ..do (1 mole) 2-(4-hydroxy3"carb0xypl1eny1amino)-5- Cu Do.

naphthol-7-sulfonic acid and (1 mole) 1-(4"l1ydroxy-3-ca1'boxybenzene-sulionylamino)-8-naplitliol- 3:6-disulionic acid.

74 Disuliuric acid semi-ester of 4:4-diliydroxy-3:3- 1-(4-hydroxy-3-carboxybcnzene-sulionyl-amino)-8- Cu Violet.

diamiuodiphenyl. naphthol-3:6-disulfonie acid.

d .d 60 Dull violet.

.do Do. 1-(2-hydroxy-3-carboxyphcnyl)-3-metl1yl-5 pyraz0 Brown.

lone-5-sulfonic acid. 78 4:4-dihydroxy-3:3-diaminodiphcnylsulfone 2-(4-hydroxy-3-carboxybenzcnc-sulfonylamino) -8- Cr Reddish grey.

naphthol-G-sulionic acid. 79.- Disuliuric acid semi-ester oi 2:2(4:4-di-hydroxy-3: 1-(4-hydroxy-3-carboxybenzenc-sulionyl-amino)-8- Cu Violet.

3"-dian1ino-diphcnyl)-pr0pane. napl1thol-3,6-disulionic acid. D

Dull violet. Do. -hy oxy-3-carboxyplienyl)-3-mcthyl-5-pyrazo- Cu Violet.

lone-5-sulfonic acid.

84 do 1-[4-(4-hydroxy-3"-cai'boxy-bcnzcnesulfonylamino) Cu Blue.

benzoylamino]-8-napl1thol-4:6-disulfonic acid.

85 4:4-diaminodiphenylamino-Z-sulionic acid 2-(4-hydr0xy-3-carboxybenzene-sulionylamino)-5- Cu Dull violet.

naphthol-7-sulfonic acid.

1. A compound of the formula References Cited UNITED STATES PATENTS 1,953,512 4/1934 Sieglitz et a1. 260178 2,204,230 6/1940 Rossander et al. 260l44 2,404,198 7/1946 Straub et al. 260147 2,439,153 4/1948 Straub et a1. 260 -161 2,753,335 7/1956 Wehrli 260148 CHARLES B. PARKER, Primary Examiner DONALD M. PAPUGA, Assistant Examiner US. Cl. X.R.

COOll 

